Rubbery polymer

ABSTRACT

There is a need for polymers which are utilized in automotive interiors which offer increased heat and ultraviolet light resistance. It is particularly critical for polymers which are utilized in making skin compounds for automotive instrument and door panels to display excellent heat and ultraviolet light resistance. This invention discloses a rubbery polymer which can be blended with polyvinyl chloride to make leathery compositions having good heat and ultraviolet light resistance, said rubbery polymer being comprised of repeat units which are comprised of (a) butyl acrylate, or optionally a mixture of butyl acrylate and 2-ethylhexyl acrylate containing up to about 40% 2-ethylhexyl acrylate, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate, (c) acrylonitrile, (d) styrene, (e) a half ester maleate soap, and (f) a crosslinking agent. Such leathery compositions offer an excellent combination of properties for utilization in making skin compounds for panels used in automotive applications.

This is a Divisional of application Ser. No. 08/306,291, filed on Sep.15, 1994, now U.S. Pat. No. 5,415,940 presently pending which is aDivisional of application Ser. No. 08/043,076, filed on Apr. 5, 1993,now issued as U.S. Pat. No. 5,380,785.

BACKGROUND OF THE INVENTION

Automotive instrument panels and door panels are typically compositeswhich are made of a rigid backing which supports a semi-rigid urethanefoam with the semi-rigid urethane foam being covered with a skincompound. Such skin compounds are typically blends of polyvinyl chloride(PVC) with a nitrile rubber (NBR). The nitrile rubber is included insuch blends as a permanent modifier for the PVC which provides it with ahigher degree of flexibility.

The automotive industry is currently moving toward more aerodynamic bodydesigns which typically include larger glass areas. Such design changeshave significantly increased the heat and ultraviolet light agingrequirements of automotive interiors. This has in turn significantlyincreased the demands put upon the polymers which are utilized as skinsin automotive interior panels.

Heat and light stabilizers can be employed to improve the heat andultraviolet light aging characteristics of conventional PVC/NBR blendswhich are utilized as skins for automotive interior panels. However, thedegree to which the aging characteristics of such blends can be improvedby the addition of additives is limited. In fact, there is a demand forperformance characteristics in such applications which heretofore hasnot been realized by the utilization of heat and light stabilizers. Forinstance, it would be highly desirable for the skins used in automotivepanels to resist discoloration and cracking under conditions of highheat and intense ultraviolet light throughout the life of the vehicle.

NBR/PVC blends offer an array of physical properties which make themuseful as a skin composition for automotive panels. The NBR acts as apermanent flexibilizing monomer for the PVC. It also acts as a shrinkagecontrol agent, and embossing aid, and improves grain retention. The NBRin such blends further provides vacuum forming gauge control andexhibits low fog characteristics. NBR is highly compatible with PVC andhas the capability of being recycled. It is essential for any polymerwhich is substituted for NBR to display these essential characteristics.

SUMMARY OF THE INVENTION

The present invention relates to a rubbery polymer which can be blendedwith PVC to make leathery compositions. These compositions areparticularly useful in manufacturing skins for automotive interiorpanelling. Skin compositions which are made utilizing this rubberypolymer provide a higher level of resistance to heat and ultravioletlight than those made utilizing conventional NBR/PVC blends. The rubberypolymers of this invention also offer low fog characteristics, low odor,shrinkage control, and grain retention. They also act as an embossingaid and as a permanent flexibilizing modifier. The rubbery polymers ofthis invention also have characteristics which make them useful inbuilding gasket applications.

This invention more specifically discloses a rubbery polymer which canbe blended with polyvinyl chloride to make leathery compositions havinggood heat and ultraviolet light resistance, said rubbery polymer beingcomprised of repeat units which are comprised of (a) butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining up to about 40% 2-ethylhexyl acrylate, (b) at least onemember selected from the group consisting of methyl methacrylate, ethylmethacrylate, methyl acrylate, and ethyl acrylate, (c) acrylonitrile,(d) styrene, (e) a half ester maleate soap, and (f) a crosslinkingagent.

The subject invention further reveals a process for preparing a rubberypolymer which can be blended with polyvinyl chloride to make leatherycompositions having good heat and ultraviolet light resistance, saidprocess comprising the steps of (1) polymerizing (a) butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining up to about 40% 2-ethylhexyl acrylate, (b) at least onemember selected from the group consisting of methyl methacrylate, ethylmethacrylate, methyl acrylate, and ethyl acrylate, (c) acrylonitrile,and (d) a crosslinking agent under emulsion polymerization conditions toproduce a seed polymer containing latex; (2) adding (a) styrene, (b)additional acrylonitrile, and (c) additional crosslinking agent to theseed polymer containing latex under emulsion polymerization conditionswhich result in the formation of an emulsion containing the rubberypolymer; and (3) recovering the rubbery polymer from the emulsioncontaining the rubbery polymer.

The present invention also discloses a leathery composition which isuseful in automotive applications which is comprised of (1) polyvinylchloride, (2) a plasticizer, and (3) a rubbery polymer which iscomprised of repeat units which are comprised of (a) butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining up to about 40% 2-ethylhexyl acrylate, (b) at least onemember selected from the group consisting of methyl methacrylate, ethylmethacrylate, methyl acrylate, and ethyl acrylate, (c) acrylonitrile,(d) styrene, (E) a half ester maleate soap, and (f) a crosslinkingagent.

The subject invention further reveals a panel for automotiveapplications which is comprised of a semirigid urethane foam which issupported by a rigid backing, wherein said semirigid urethane foam iscovered with a leathery skin which is comprised of (1) polyvinylchloride, (2) a plasticizer, and (3) a rubbery polymer which iscomprised of repeat units which are comprised of (a) butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining up to about 40% 2-ethylhexyl acrylate, (b) at least onemember selected from the group consisting of methyl methacrylate, ethylmethacrylate, methyl acrylate, and ethyl acrylate, (c) acrylonitrile,(d) styrene, (e) a half ester maleate soap, and (f) a crosslinkingagent.

DETAILED DESCRIPTION OF THE INVENTION

The rubbery polymers of this invention are synthesized utilizing a freeradical emulsion polymerization technique. These rubbery polymers arecomprised of repeat units which are derived from (a) butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining up to about 40% 2-ethylhexyl acrylate, (b) methylmethacrylate, ethyl methacrylate, methyl acrylate, or ethyl acrylate,(c) acrylonitrile, (d) styrene, (e) a half ester maleate soap, and (f) acrosslinking agent. The crosslinking agent is typically amulti-functional acrylate, a multi-functional methacrylate ordivinylbenzene. Some specific examples of crosslinking agents which canbe used include ethylene glycol methacrylate, divinylbenzene, and1,4-butanediol dimethacrylate.

Technically, the rubbery polymers of this invention Contain repeat units(chain linkages) which are derived from (a) butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining up to about 40% 2-ethylhexyl acrylate, (b) methylmethacrylate, ethyl methacrylate, methyl acrylate, or ethyl acrylate,(c) acrylonitrile, (d) styrene, (e) a half ester maleate soap, and (f) acrosslinking agent. These repeat units differ from the monomers thatthey were derived from in that they contain one less carbon-carbondouble bond than is present in the respective monomer. In other words, acarbon-to-carbon double bond is consumed during the polymerization ofthe monomer into a repeat unit in the rubbery polymer. Thus, in sayingthat the rubbery polymer contains various monomers in actuality meansthat it contains repeat units which are derived from those monomers.

The rubbery polymers of this invention will normally contain (a) fromabout 40 weight percent to about 80 weight percent butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining up to 40 weight percent 2-ethylhexyl acrylate, (b) from about5 weight percent to about 35 weight percent methyl methacrylate, ethylmethacrylate, methyl acrylate, or ethyl acrylate, (c) from about 4weight percent to about 30 weight percent acrylonitrile, (d) from about3 weight percent to about 25 weight percent styrene, (e) from about 0.5weight percent to about 8 weight percent of a half ester maleate soap,and (f) from about 0.25 weight percent to about 8 weight percent of acrosslinking agent.

Such rubbery polymers will preferably contain (a) from about 50 weightpercent to about 80 weight percent butyl acrylate, or optionally amixture of butyl acrylate and 2-ethylhexyl acrylate containing up toabout 40% 2-ethylhexyl acrylate, (b) from about 3 weight percent toabout 25 weight percent of at least one member selected from the groupconsisting of methyl methacrylate, ethyl methacrylate, methyl acrylate,and ethyl acrylate, (c) from about 6 weight percent to about 30 weightpercent acrylonitrile, (d) from about 5 weight percent to about 18weight percent styrene, (e) from about 1 weight percent to about 5weight percent of a half ester maleate soap, and (f) from about 0.5weight percent to about 4 weight percent of a crosslinking agent. Therubbery polymers of this invention will more preferably be comprised ofrepeat units which are derived from (a) from about 55 weight percent toabout 75 weight percent butyl acrylate, or optionally a mixture of butylacrylate and 2-ethylhexyl acrylate containing up to about 40%2-ethylhexyl acrylate, (b) from about 5 weight percent to about 20weight percent of at least one member selected from the group consistingof methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethylacrylate, (c) from about 10 weight percent to about 25 weight percentacrylonitrile, (d) from about 8 weight percent to about 14.weightpercent styrene, (e) from about 2 weight percent to about 4 weightpercent of a half ester maleate soap, and (f) from about 1 weightpercent to about 3 weight percent of a crosslinking agent. Thepercentages reported in this paragraph are based upon the total weightof the rubbery polymer.

The rubbery polymers of the present invention are synthesized in anaqueous reaction mixture by utilizing a free radical polymerizationtechnique. The reaction mixture utilized in this polymerizationtechnique is comprised of water, the appropriate monomers, a suitablefree radical initiator, a crosslinking agent, a half ester maleate soap,and a metal salt of an alkyl sulfonate or a metal salt of an alkylsulfate. The reaction mixture utilized in this polymerization techniquewill normally contain from about 10 weight percent to about 80 weightpercent monomers, based upon the total weight of the reaction mixture.The reaction mixture will preferably contain from about 20 weightpercent to about 70 weight percent monomers and will more preferablycontain from about 40 weight percent to about 50 weight percentmonomers.

The reaction mixtures utilized in carrying out such polymerizations willtypically contain from about 0.005 phm (parts per hundred parts ofmonomer by weight) to about 1 phm of at least one member selected fromthe group consisting of metal salts of alkyl sulfates and metal salts ofalkyl sulfonates. It is generally preferred for the reaction mixture tocontain from about 0.008 phm to about 0.5 phm of the metal salt of thealkyl sulfonate or the metal salt of the alkyl sulfate. It is normallymore preferred for the reaction mixture to contain from about 0.05 phmto about 0.3 phm of the metal salt of the alkyl sulfonate or the metalsalt of the alkyl sulfate.

The free radical polymerization technique utilized in this synthesis isnormally initiated by including a free radical initiator in the reactionmixture. Virtually, any type of compound capable of generating freeradicals can be utilized as the free radical initiator. The free radicalgenerator is normally employed at a concentration within the range ofabout 0.01 phm to about 1 phm. The free radical initiators which arecommonly used include the various peroxygen compounds such as potassiumpersulfate, ammonium persulfate, benzoyl peroxide, hydrogen peroxide,di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide,decanoyl peroxide, lauryl peroxide, cumene hydroperoxide, p-menthanehydroperoxide, t-butyl hydroperoxide, acetyl peroxide, methyl ethylketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate,t-butyl peroxyacetate, t-butyl peroxymaleic acid, t-butylperoxybenzoate, acetyl cyclohexyl sulfonyl peroxide, and the like; thevarious azo compounds such as 2-t-butylazo-2-cyanopropane, dimethylazodiisobutyrate, azodiisobutylronitrile,2-t-butylazo-1-cyanocyclohexane, 1-t-amylazo-l-cyanocyclohexane, and thelike, the various alkyl perketals, such as2,2-bis-(t-butyloperoxy)butane, and the like. Water soluble peroxygenfree radical initiators are especially useful in such aqueouspolymerizations.

The emulsion polymerizations of this invention are typically carried outat the temperature ranging between about 60° F. (20° C.) and 190° F.(88° C.). At temperatures above about 88° C. alkyl acrylate monomers,such as butyl acrylate, have a tendency to boil. Thus, a pressurizedjacket would be required for heating such alkyl acrylate monomers totemperatures in excess of about 88° C. On the other hand, atpolymerization temperatures of less than about 55° C. a redox initiatorsystem is required to insure satisfactory polymerization rates.

The sulfonate surfactants that are useful in this invention arecommercially available from a wide variety of sources. For instance, DuPont sells sodium alkylarylsulfonate under the tradename Alkanol™,Browning Chemical Corporation sells sodium dodecylbenzene sulfonatesunder the tradename Ufaryl™ Dl-85, and Ruetgers-Nease Chemical Companysells sodium cumene sulfonate under the tradename Naxonate Hydrotrope™.Some representative examples of sulfonate surfactants which can be usedinclude sodium toluene-xylene sulfonate, sodium toluene sulfonate,sodium cumene sulfonates, sodium decyldiphenylether sulfonate, sodiumdodecylbenzenesulfonate, sodium dodecyldiphenylether sulfonate, sodium1-octane sulfonate, sodium tetradecane sulfonate, sodium pentadecanesulfonate, sodium heptadecane sulfonate, and potassium toluenesulfonate.

Metal salts of alkylbenzene sulfonates are a highly preferred class ofsulfonate surfactant. The metal will generally be sodium or potassiumwith sodium being preferred. Sodium salts of alkylbenzene sulfonateshave the structural formula: ##STR1## wherein R represents an alkylgroup containing from 1 to about 20 carbon atoms. It is preferred forthe alkyl group to contain from about 8 to about 14 carbon atoms.

The free radical emulsion polymerization utilized in synthesizing therubbery polymers of this invention are typically conducted at atemperature which is within the range of about 10° C. to about 95° C. Inmost cases, the polymerization temperature utilized will vary betweenabout 20° C. and about 80° C. The polymerization is carried out as a twostep batch process. In the first step, a seed polymer containing latexis synthesized. This is done by polymerizing (a) butyl acrylate, oroptionally a mixture of butyl acrylate and 2-ethylhexyl acrylatecontaining-up to about 40% 2-ethylhexyl acrylate, (b) at least onemember selected from the group consisting of methyl methacrylate, ethylmethacrylate, methyl acrylate, and ethyl acrylate, (c) acrylonitrile,and (d) a crosslinking agent.

The seed polymer containing latex is typically prepared by thepolymerization of a monomer mixture which contains about 40 to about 90weight percent butyl acrylate, or optionally a mixture of butyl acrylateand 2-ethylhexyl acrylate containing up to about 40% 2-ethylhexylacrylate, from about 5 to about 35 weight percent methyl methacrylate,ethyl methacrylate, methyl acrylate, or ethyl acrylate, from about 2 toabout 30 weight percent acrylonitrile, and from about 0.25 weightpercent to 6 weight percent of the crosslinking agent. It is typicallypreferred for the monomeric component utilized in the first step toinclude about 50 weight percent to about 85 weight percent butylacrylate, or optionally a mixture of butyl acrylate and 2-ethylhexylacrylate containing up to about 40% 2-ethylhexyl acrylate, from about 5weight percent to about 30 weight percent ethyl acrylate, ethylmethacrylate, methyl acrylate, or methyl methacrylate, from about 4weight percent to about 28 weight percent acrylonitrile, and from about0.5 weight percent to about 4 weight percent of the crosslinking agent.It is generally more preferred for the monomer charge composition usedin synthesizing the seed polymer latex to contain from about 60 weightpercent to about 80 weight percent butyl acrylate, or optionally amixture of butyl acrylate and 2-ethylhexyl acrylate containing up toabout 40% 2-ethylhexyl acrylate, from about 5 weight percent to about 25weight percent methyl methacrylate, ethyl methacrylate, methyl acrylate,or ethyl acrylate, from about 5 weight percent to about 25 weightpercent acrylonitrile, and from about 1 to about 3 weight percentcrosslinking agent.

After the seed polymer latex has been prepared, styrene monomer,additional acrylonitrile monomer, and additional crosslinking agent isadded to the seed polymer containing latex. As a general rule, fromabout 4 parts by weight to about 30 parts by weight of styrene, fromabout 1 part by weight to about 20 parts by weight of additionalacrylonitrile, and from about 0.01 to 2 parts by weight of thecrosslinking agent will be added. In this second stage of thepolymerization, it is preferred to add from about 6 parts by weight toabout 22 parts by weight of styrene, from about 3 parts by weight toabout 12 parts by weight of acrylonitrile, and from about 0.05 parts byweight to 1 part by weight of the crosslinking agent. It is typicallymore preferred for from about 10 parts by weight to about 17 parts byweight of styrene, from about 4 parts by weight to about 8 parts byweight of acrylonitrile, and from about 0.1 parts by weight to about 0.5parts by weight of the crosslinking agent to be added to the seedpolymer latex to initiate the second phase of the polymerization.

A wide variety of crosslinking agents can be utilized in carrying outthe polymerizations of this invention. Some representative examples ofcrosslinking agents which can be utilized include difunctionalacrylates, difunctional methacrylates, trifunctional acrylates,trifunctional methacrylates, and divinylbenzene. 1,4-butanedioldimethacrylate has proven to be particularly useful as the crosslinkingagent.

In most cases, the polymerization will be continued until a high monomerconversion has been attained. At this point, the rubbery polymer made bythe two step batch polymerization process is recovered from the emulsion(latex). This can be accomplished by utilizing standard coagulationtechniques. For instance, coagulation can be accomplished by theaddition of salts, acids, or both to the latex.

The half ester maleate soap utilized in the polymerization is preparedby reacting maleic anhydride with a fatty alcohol containing from about10 to about 24 carbon atoms. It is typically preferred to utilize afatty alcohol which contains from about 12 to about 16 carbon atoms. Onemole of the maleic anhydride is reacted with one mole of the fattyalcohol in producing the half ester maleate soap. This reaction istypically conducted at a temperature which is within the range of about50° C. to about 80° C. and can be depicted as follows: ##STR2## Sodiumhydroxide or potassium hydroxide is then typically added to make thehalf ester maleate soap. This step can be depicted as follows: ##STR3##

After the rubbery polymer is recovered by coagulation, it is dried. Itis sometimes advantageous to convert the rubbery polymer into a powderto facilitate its usage. In this case, it will be beneficial to add apartitioning agent to the rubbery polymer. Some representative examplesof partitioning agents which can be employed include calcium carbonate,emulsion polyvinyl chloride, and silica. Calcium carbonate is a highlydesirable partitioning agent which can be utilized in such applications.

The rubbery polymers of this invention can be blended withpolyvinylchloride to make leather like compositions. These leatherycompositions Offer an excellent combination of properties forutilization in making skin compounds for panels used in automotiveapplications. These leathery compositions can be prepared by blendingthe rubbery polymer into polyvinylchloride (PVC) utilizing standardmixing techniques. It is highly preferred for the rubbery polymer to bein powdered form when blended into PVC to make such leatherycompositions.

A wide variety of plasticizers which are compatible with the polyvinylchloride resins can be employed. Some representative examples ofplasticizers which are highly suitable for this application includeabietic derivatives, such as hydroabietyl alcohol, methyl abietate andhydrogenated methyl abietate; acetic acid derivatives, such ascumylphenyl acetate; adipic acid derivatives, such as benzyloctyladipate, dibutyl adipate, diisobutyl adipate, di-(2-ethylhexyl) adipate,diisononyl adipate, diisooctylo adipate, dinonyl adipate, C₇₋₉ linearadipate, dicapryl adipate, octyl decyl, adipate (n-octyl, n-decyladipate), straight chain alcohol adipate, didecyl adipate (diisodecyladipate), dibutoxyethyl adipate, high molecular weight adipate,polypropylene adipate, modified polypropylene adipate; azelaic acidderivatives, such as dicyclohexyl azelate, di-(2-ethylhexyl) azelate,di-n-hexyl azelate, low temperature plasticizer, diisooctyl azelate;benzoic acid derivatives such as diethylene glycol dibenzoate,dipropylene glycol dibenzoate, diethylene glycol benzoate anddipropylene glycol benzoate blend, proprietary low stain, neopentylglycol dibenzoate, glyceryl tribenzoate, timethylolethane tribenzoate,pentaerylthritol tribenzoate, cumylphenyl benzoate; polyphenylderivatives such as hydrogenated terphenyl; citric acid derivatives,such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate,acetyl tri-n-butyl citrate, acetal tributyl citrate; epoxy derivativessuch as butyl epoxy stearate, epoxy-type plasticizer, epoxy-typeplasticizer tallate, alkyl epoxy stearate, epoxidized butyl ester,epoxidized octyl tallage, epoxidized soybean oil, epoxidizedtriglyceride, epoxidized soya bean oil, epoxidized sunflower oil,epoxidized-type plasticizer, epoxidized linseed oil, epoxidized tallateester, 2-ethylhexylepoxy tallate, octyl epoxy stearate; proprietaryesters such as proprietary ester and mixed ester; ether derivatives,such as cumylphenyl benzyl ether; formal derivatives such as butylcarbitol formal; fumaric acid derivatives, such as dibutyl fumarate,diisooctyl fumarate, dioctyl fumarate; glutaric acid derivatives such asmixed dialkyl glutarates and dicumylphenyl glutarate; glycol derivativessuch as diethylene glycol dipelargonate, triethylene glycoldipelargonate, triethylene glycol di-(2-ethylbutyrate), triethyleneglycol di-caprylatecaprate, triethylene glycol di-(2-ethylhexoate),triethylene glycol dicaprylate, tetraethylene glycol dicaprylate,polyethylene glycol di-(2-ethylhexoate), butyl phthalyl butyl glycolate,triglycolester of vegetable oil fatty acid, triethylene glycol ester offatty acid; linear dibasic acid derivatives such as mixed dibasic ester;petroleum derivatives such as aromatic hydrocarbons; isobutyric acidderivatives such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate;isophthalic acid derivatives such as di(2-ethylhexyl) isophthalate,diisooctyl isophthalate, dioctylisophthalate; lauric acid derivativessuch as butyllaurate, 1,2-propylene glycol monolaurate, ethylene glycolmonoethyl ether laurate, ethylene glycol monobutyl ether laurate,glycerol monolaurate, polyethylene glycol-400-dilaurate; mellitates suchas n-octyl, n-decyl trimellitate, tri-n-octyl-n-decyl trimellitate,triisononyl trimellitate, triisooctyl trimellitate, tricapryltrimellitate, diisooctyl monoisodecyl trimellitate, triisodecyltrimellitate, tri(C₇₋₉ alkyl) trimellitate, tri-2-ethylhexyltrimellitate; nitrile derivatives such as fatty acid nitrile; oleic acidderivatives such as butyl oleate, 1,2-propylene glycol mono oleate,ethylene glycol monobutyl ether oleate, tetrahydrofurfuryl oleate,glyceryl monoleate; paraffin derivatives such as chlorinated paraffins,diethylene glycol dipelargonate, triethylene glycol dipelargonate,2-butoxyethyl dipelargonate; phenoxy plasticizers such as acetylparacumyl phenol; phosphoric acid derivatives such as tri-(2-ethylhexyl)phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyldiphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate,alkyl aryl phosphates, diphenyl-xylenyl phosphate, phenylisopropylphenyl phosphate; phthalic acid derivatives such as alkylbenzene phthalates, dimethyl phthalate, dibutyl phthalate, diisobutylphthalate, dihexyl phthalate, butyl octyl phthalate, butyl isodecylphthalate, butyl iso-hexyl phthalate, diisononyl phthalate, dioctylphthalate, di-(2-ethyl hexyl) phthalate, n-octyl-n-decyl phthalate,hexyl octyl decyl phthalate, didecyl phthalate diisodecyl phthalate,diisodecyl phthalate, diundecyl phthalate, butyl-ethylhexyl phthalate,butylbenzyl phthalate, octylbenzyl phthalate, dicyclohexyl phthalate,diphenyl phthalate, alkylaryl phthalates and 2-ethylhexylisodecylphthalate; ricinoleic acid derivatives such as methylacetyl ricinoleate,n-butyl acetyl ricinoleate, glyceryl triacetyl ricinoleate; sebacic acidderivatives such as dimethyl sebacate, dibutyl sebacate, anddibutoxyethyl sebacate; stearic acid derivatives such as glyceryltri-acetoxy stearate, butyl acetoxy stearate, methylpentachlorostearate,and methoxylethyl acetoxy stearate; sucrose derivatives such as sucrosebenzoate; sulfonic acid derivatives such as alkylsulfonic esters ofphenol; tall oil derivatives such as methylester of tall oil andisooctyl ester of tall oil; and terephthalic acid derivatives such asdioctyl terephthalate.

Such leathery compositions typically contain from about 40 to 160 partsby weight of the rubbery polymer, from about 10 to about 50 parts of aplasticizer, and from about 0.1 to about 5 parts by weight of anantidegradant per 100 parts by weight of the polyvinylchloride. It istypically preferred for such leathery compositions to contain from about60 to about 120 parts by weight of the rubbery polymer, from about 15 toabout 40 parts of the plasticizer, and from about 0.5 to 3 parts of anantidegradant (per 100 parts of the PVC). It is typically more preferredfor the leathery composition to contain from about 70 to about 90 partsby weight of the rubbery polymer, from about 20 to about 30 parts byweight of the plasticizer, and from about 1 to 2 parts by weight of theantidegradant per 100 parts by weight of the PVC.

Such compositions will also generally contain anacrylonitrile-butadiene-styrene resin (ABS resin). The leatherycomposition will typically contain from about 15 parts to about 80 partsof ABS resin per 100 parts of PVC. The leathery composition willpreferably contain from about 25to about 55 parts per weight of the ABSresin per 100 parts by weight of the PVC. It is generally more preferredfor the leathery composition to contain from about 30 to about 40 partsby weight of the ABS resin per 100 parts by weight of PVC. Variouscolorants and/or pigments will typically also be added to thecomposition to attain a desired color.

The leathery compositions of this invention are useful in a wide varietyof applications. For example, they have been found to be extremelyvaluable when used in making skins for automotive panels. Such panelsare typically comprised of a semi-rigid urethane foam which is supportedby a rigid backing and covered with the leathery composition of thisinvention. Such skins are made by calendering the leathery compositionsof this invention and then cutting them to the desired size and shape.Such skins for automotive applications which are made with the leatherycompositions of this invention offer outstanding heat and ultravioletlight stability. These are highly desirable characteristics which canhelp to prevent the skin of automotive panels from cracking during thenormal life of the vehicle.

The rubbery polymers of this invention can also be blended with otherhalogen containing polymers (in addition to PVC), styrenic polymers(polymers which contain styrene, such as acrylonitrile-styrene-acrylate(ASA) polymers), polyolefins, and polyamides to produce compositionswhich exhibit good heat and ultraviolet light resistance. Such polymericcompositions can be used in manufacturing a wide variety of usefularticles, such as profiles, mouldings, sheeting, flooring, wallcoverings, hose, cables, and footwear. Virtually any type of polyamide(nylon) can be utilized in preparing such blends. These nylons aregenerally prepared by reacting diamines with dicarboxylic acids. Thediamines and dicarboxylic acids which are utilized in preparing suchnylons will generally contain from about 2 to about 12 carbon atoms.However, nylons which can be utilized in such blends can also beprepared by addition polymerization. Some representative examples ofnylons which can be used include nylon-6,6, nylon-6, nylon-7, nylon-8,nylon-9, nylon-10, nylon-11, nylon-12 and nylon-6,12. These nylons willtypically have a number average molecular weight which is within therange of about 8,000to about 40,000 and will more typically have anumber average molecular weight which is within the range of about10,000 to about 25,000. Some representative examples of polyolefinswhich can be used include linear low density polyethylene, high densitypolyethylene, polypropylene, polybutylene, and modified polyolefins,such as ethylene vinyl acetate (EVA).

This invention is illustrated by the following examples which are merelyfor the purpose of illustration and are not to be regarded as limitingthe scope of this invention or the manner in which it can be practiced.Unless specifically indicated otherwise, all parts and percentages aregiven by weight.

EXAMPLE 1

In this experiment a rubbery polymer was made utilizing the techniquesof this invention. The polymerization was conducted in a reactor havinga capacity of 100 liters. The reactor was equipped with an axially flowturbine agitator which was operated at 110 rpm (revolutions per minute).

The reactor was charged with 74.6 kg (kilograms) of water, 0.92 kg of ahalf ester maleate soap (made with C₁₆ fatty alcohol), 0.31 kg of a 50percent aqueous potassium hydroxide solution, 0.062 kg of sodiumdodecylbenzene sulfonate, 18.0 kg of n-butylacrylate, 2.6 kg ofacrylonitrile, 5.1 kg of methylacrylate, 0.38 kg of 1,4-butane dioldimethacrylate, 0.078 kg of t-dodecylmercaptan, and 0.058 kg ofpotassium persulfate. A temperature of about 60° C. was maintainedthroughout the polymerization. When a total solids content of about 25percent was achieved, 0.025 kg of additional potassium persulfate wasadded. This first stage of the polymerization was carried out for aperiod of about 21/2 hours. This first stage polymerization resulted inthe production of a seed polymer latex which was used in the second stepof the polymerization.

In the second step of the polymerization, 1.47 kg of acrylonitrile, 3.4kg of styrene, 0.050 kg of divinylbenzene, and 0.009 kg oft-dodecylmercaptan were charged into the reactor containing the seedpolymer latex. The polymerization proceeded until a solids content ofabout 30 percent was attained. The latex produced was white in color,had a pH of about 6.5, had a Brookfield viscosity of about 6 centipoise(CPS), a surface tension of about 49 dyne per centimeter, a particlesize of about 80 nanometers, and had a residual acrylonitrileconcentration of about 2,000 ppm (parts per million). The latex made wascoagulated and a dry rubber was recovered.

EXAMPLE 2

In this experiment a leathery composition was made by blending therubbery polymer synthesized in Example 1 into PVC resin. This blend wasprepared by blending 35 parts of ABS resin, 80 parts of the rubberypolymer, 25 parts of a plasticizer, 1.5 parts of antidegradants, and 4.5parts of a red color dispersion stabilizer into 100 parts of the PVCresin.

An oil heated Farrel 8 inch (20.3 cm) plastics mill operated at 176° C.(349° F.) was used for the compound preparation. All powders, liquids,and stabilizers were first blended in a Hobart mixer to form a rough dryblend. The dry blend and elastomer were banded on the mill and mixed for15 minutes before sheeting out at 0.040±5 gauge. Testing was conductedon milled sheet specimens.

The leathery composition prepared was determined to have physicalcharacteristics which made it highly suitable for utilization in makingskin compounds for panels used in automotive applications. The tensilestrength, elongation to break, 100 percent modulus and Shore D hardnessof the leathery composition made is reported in Table I (Example 2). Theleather composition was also evaluated to determine its heat andultraviolet light stability. The light aging studies were conducted in aQ-U-V accelerated weathering tester which was equipped with a UVB-313lamp. One aging cycle consisted of 6 hours of light and 4 hours of 100percent humidity at 65° C. with continuous repeated cycles to the totalhours reported in Table I. The samples were 1 inch (2.54 cm)×3 inches(7.62 cm) in size.

Heat aging was conducted by the ASTM 573-78 air oven heat aging methodwith ASTMdie C specimens. Tensile properties were determined before andafter aging with a United Model FM30-DM1VA tensile tester at 20 inchesper minute (50.8 cm/minutes) crosshead speed, 2.5 inch. (6.35 Cm) jawseparation, and 1 inch (2.54 cm) benchmark.

COMPARATIVE EXAMPLES 3-4

In this experiment, conventional skin compounds were prepared forcomparative purposes. In these experiments, the same procedure as wasdescribed in Example 2 was employed, except for the fact that an ASAresin was substituted for the rubbery polymer utilized in Example 2.These ASA resins were terpolymers of acrylonitrile, styrene, and anacrylate monomer. In Comparative Example 3, the ASA resin used was MobayBaymod™ KU3-2069AASA resin with Baymod™ KU3-2079AASA resin beingutilized in Comparative Example 4.

The physical properties of these conventional skin compounds and theirheat and ultraviolet light resistance characteristics are compared tothose of the leathery compositions of this invention in Table I.

COMPARATIVE EXAMPLE 5

In this experiment an additional conventional skin compound was preparedfor comparative purposes. In this experiment the same procedure as wasdescribed in Example 2 was employed, except for the fact that acrosslinked nitrile rubber was substituted for the rubbery polymerutilized in Example 2 and except for the fact that the amount of ABSresin employed was increased to 60 parts. The physical properties of theconventional skin compound prepared in this experiment and its heat andultraviolet light resistance characteristics are compared to those ofthe leathery compositions of this invention in Table I.

                  TABLE I    ______________________________________    COMPOUND      Ex. 2   Ex. 3*   Ex. 4* Ex. 5*    ______________________________________    Tensile, MPa  17.4    21.7     22.8   20.2    % Elongation  125     197      116    296    100% Modulus, MPa                  17.2    --       22.6   16.9    Shore D Hardness                  60      67       70     62    Air oven Aged @ 110 °C., % E Change    504 Hours     0       -25.6    -37    -20    1008 Hours    -29     -23.9    -78    -67    1512 Hours    -28     -26.2    -80    -90    1992 Hours    -34     -52      -95    Air Oven Aged @ 121° C., % E Change    70 Hours      0       0        -71    -12    144 Hours     -3      -9.4     -79    -10    288 Hours     -15     -11      -76    -70    384 Hours     -20     -11.1    -75    -94    480 Hours     -42     -35.8    -96    -82    528 Hours     -44     -37.6    -98    -95    QUV 313 Light Aging Color Change    70 Hours      0.9     3.6      3.9    2.7    200 Hours     7.9     8.5      7.1    9.0    360 Hours     16.5    18.8     18.6   18.2    540 Hours     16.5    19.1     21.5   20.9    ______________________________________     *Examples 3, 4, and 5 are Comparative Examples

As can be seen by reviewing the data in Table I, the physical propertiesof the leathery composition made with the rubbery polymer of thisinvention were very comparable to the standard skin compounds shown inComparative Examples 3, 4 and 5. However, the skin compound madeutilizing the rubbery polymer of this invention had greatly improvedheat aged characteristics after 1,992 hours at 110° C. Its heatresistance 121° C. proved to be comparable to the heat stabilitydisplayed in Comparative Example 3. However, the skin compound madeutilizing the rubbery polymer of this invention had greatly improvedheat resistance at 121° C. as compared to the skin compound made inComparative Example 4 and in Comparative Example 5. The leatherycomposition made in Example 2 proved to be superior to both of thestandard skin compounds made in Comparative Examples 3, 4, and 5. Thus,the skin compounds of this invention display greater resistance toultraviolet light than do conventional skin compounds made with ASAresins.

EXAMPLE 6

In this experiment a rubbery polymer was synthesized utilizing aprocedure similar to the procedure employed in Example 1. Thispolymerization was conducted in a reactor having a capacity of 100liters. The reactor was equipped with an axially flow turbine agitatorwhich was operated at 110 rpm. The reactor was initially charged with70.92 kg of water, 0.87 kg of dodecanol monomaleate, 0.40 kg of anaqueous 50% solution of potassium hydroxide, 0.06 kg of sodiumdodecylbenzene sulfonate, 0.06 kg of sodium pyrophosphate, 0.05 kg oftriethanol amine, 22.13 kg of n-butyl acrylate, 2.60 kg ofacrylonitrile, 1.30 kg of methyl methacrylate, 0.65 kg of 1,4-butanedioldimethacrylate, 0.08 kg of t-docecylmercaptan, and 1.56 kg of a 5%solution of potassium persulfate. A temperature of about 35° C. wasmaintained throughout the polymerization. When a total solids content ofabout 24 percent was achieved, 0.52 kg of additional potassiumpersulfate solution was added. This first stage of the polymerizationwas carried out for a period of about 21/2 hours. This first stagepolymerization resulted in the production of a seed polymer latex whichwas used in the second step of the polymerization.

In the second step of the polymerization, 1.49 kg of acrylonitrile, 3.47kg of styrene, 0.050 kg of divinylbenzene, and 9.3 mg oft-dodecylmercaptan were charged into the reactor containing the seedpolymer latex. The polymerization temperature was then raised to 70° C.and the polymerization was allowed to continue. After the polymerizationwas completed, the latex made was coagulated and a dry rubber wasrecovered.

EXAMPLE 7

In this experiment a rubbery polymer was made in a 2 liter glass reactorutilizing the technique of this invention. In the procedure employed1126 g of water, 5.93 g of a 50% aqueous potassium hydroxide solution,14.0 g of hexadecyl monomaleate, 1.0 g of a 0% solution of sodiumdodecylbenzene sulfonate, 1.0 g of sodium pyrophosphate, 231 g ofn-butyl acrylate, 105 g of acrylonitrile, 42 g of 2-ethylhexylacrylate,42 g of methyl acrylate, 8.4 g of 1,4-butanediol dimethacrylate, 0.84 gof t-dodecylmethacrylate, 8.3 g of a 5% aqueous solution of triethanolamine, and 24.9 g of a 5% aqueous solution of potassium persulfate wereinitially charged into the reactor. A temperature of about 35° C. wasmaintained during the first stage of the polymerization. When a solidscontent of about 20% was reached the reaction temperature was increasedto about 60° C. and 24 g of additional acrylonitrile, 56 g of styrene,0.96 g of divinylbenzene, and 0.16 g of t-dodecylmercaptan were chargedinto the reactor. After the polymerization was complete, the latex madewas coagulated and a rubber was recovered.

EXAMPLE 8

In this experiment a rubbery polymer was made in a 2 liter glass reactorutilizing the technique of this invention. In the procedure employed1126 g of water, 5.93 g of a 50% aqueous potassium hydroxide solution,14.0 g of hexadecyl monomaleate, 1.0 g of a 30% solution of sodiumdodecylbenzene sulfonate, 1.0 g of sodium pyrophosphate, 168 g ofn-butyl acrylate, 105 g of acrylonitrile, 105 g of 2-ethylhexylacrylate,42 g of methyl acrylate, 6.3 g of 1,4-butanediol dimethacrylate, 0.44 gof t-dodecylmethacrylate, 8.3 g of a 5% aqueous solution of triethanolamine, and 24.9 g of a 5% aqueous solution of potassium persulfate wereinitially charged into the reactor. A temperature of about 35° C. wasmaintained during the first stage of the polymerization. When a solidscontent of about 20% was reached the reaction temperature was increasedto about 60° C. and 24 g of additional acrylonitrile, 56 g of styrene,0.96 g of divinylbenzene, and 0.16 g of t-dodecylmercaptan were chargedinto the reactor. After the polymerization was completed, the latex madewas coagulated and a rubber was recovered.

EXAMPLES 9-12

In this series of experiments leathery compositions were made beblending the rubbery polymers made in Examples 1, 6, 7, and 8 into PVC.In the procedure used 40 parts of the rubbery polymer was blended into100 parts of the PVC. The blends made also included 50 parts of DOP and3 parts of Ba/Zn. The blends were made by mixing the components in amill at 180° C. for 6 minutes and then pressing them into samples at180° C. The samples made were then tested to determine their physicalproperties.

The physical properties of the samples made are reported in Table II.The blend made in Example 9 contained the rubber composition of Example1, the blend of Example 10 contained the rubber composition of Example6, the blend of Example 11 contained the rubber composition of Example7, and the blend of Example 12 contained the rubber composition ofExample 8.

                  TABLE II    ______________________________________                           Modulus           Shore A  Tensile            50%   100%    Example           Hardness Strength  Elongation                                       (MPa) (MPa)    ______________________________________    9      80       17.0 MPA  275%     5.8   9.0    10     80       16.4 MPA  258%     5.7   8.8    11     80       15.5 MPA  270%     5.2   7.8    12     80       16.3 MPA  260%     6.1   9.4    ______________________________________

As can be seen from Table II, all of the rubbery polymers made inExamples 1, 6, 7, and 8 could be made into leathery compositions whichhad good physical properties. In fact, the leathery compositions madeexhibited as excellent combination of properties for utilization inmaking skins for use in automotive interior panels, such as crash pads.

While certain representative embodiments and details have been shown forthe purpose of illustrating the subject invention, it will be apparentto those skilled in this art that various changes and modifications canbe made therein without departing from the scope of the subjectinvention.

What is claimed is:
 1. A process for preparing a rubbery polymer whichcan be blended with polyvinyl chloride to make leathery compositionshaving good heat and ultraviolet light resistance, said processcomprising the steps of (1) polymerizing (a) butyl acrylate, (b) atleast one member selected from the group consisting of methylmethacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate,(c) acrylonitrile, (d) a crosslinking agent, and (e) a half estermaleate soap under emulsion polymerization conditions to produce a seedpolymer containing latex; (2) adding (a) styrene, (b) additionalacrylonitrile, and (c) additional crosslinking agent to the seed polymercontaining latex under emulsion polymerization conditions which resultin the formation of an emulsion containing the rubbery polymer; and (3)recovering the rubbery polymer from the emulsion containing the rubberypolymer.
 2. A process as specified in claim 1 which further comprisesdrying the rubbery polymer recovered from the emulsion and subsequentlyconverting it into a powder.
 3. A process as specified in claim 2wherein the rubbery polymer is converted to a powder in the presence ofa partitioning agent.
 4. A process as specified in claim 3 wherein thepartitioning agent is selected from the group consisting of calciumcarbonate, emulsion polyvinyl chloride, and silica.
 5. A process asspecified in claim 1 wherein said polymerization is initiated in step(1) with a free radical initiator.
 6. A process as specified in claim 5wherein said polymerization is conducted in the presence of about 0.005phm to about 1 phm of at least one member selected from the groupconsisting of metal salts of alkyl sulfates and metal salts of alkylsulfonates.
 7. A process as specified in claim 6 wherein saidpolymerization is carried out at a temperature which is within the rangeof about 60° F. to about 190° F.
 8. A process as specified in claim 7wherein the crosslinking agent is 1,4-butanediol dimethacrylate.
 9. Aprocess as specified in claim 8 wherein the member selected from thegroup consisting of methyl methacrylate, ethyl methacrylate, methylacrylate, and ethyl acrylate is methyl acrylate.
 10. A process asspecified in claim 9 wherein said polymerization is conducted in thepresence of about 0.05 phm to about 0.3 phm of at least one memberselected from the group consisting of metal salts of alkyl sulfates andmetal salts of alkyl sulfonates.
 11. A process as specified in claim 7wherein said polymerization is conducted in the presence of about 0.008phm to about 0.5 phm of at least one member selected from the groupconsisting of metal salts of alkyl sulfates and metal salts of alkylsulfonates.